Chemical, physical and morphological changes in weathered coal fly ash : a case study of brine impacted wet ash dump
Fly ash is the major waste material produced by power plants in the combustion of coal to generate electricity. The main constituents of fly ash are Si, Al, Fe and Ca with smaller amount of S, Mn, Na, K, and traces of many other elements such as Co, Cd, As, Se, Zn, Mo, Pb, B, Cu and Ni. Fly ash is usually disposed either by dry or wet disposal methods. These disposal methods have raised major environmental concerns due to the potential leaching of chemical species from the ash heap by ingress of rainfall and brine used to transport the fly ash to the dam. This study focuses on the changes in chemical composition, morphology and mineral phases due to weathering, of coal fly ash co-disposed with brine over 20 years at Sasol Secunda ash dump in Mpumalanga Province, South Africa. The design and operation of the Secunda ash dump presupposes that the ash dump may act as a sink for the salts which originated from chemicals used for normal operation in the plants. The majority of these salts come from the brines generated during desalination and raw water regeneration. The aim of this study is to ascertain if the ash dump could serve as a sustainable salt sink.Samples were drawn along the depth of two drilled cores (S1 and S3) from the weathered Secunda ash dump and analysed in conjunction with the fresh (unweathered) Secunda fly ash taken from the fly ash hoppers for comparative analysis. Scanning electron microscopy (SEM), X-ray diffractive (XRD) and X-ray fluorescence (XRF) spectrometry were employed to obtain a detailed morphological, mineralogical and bulk chemical composition of all the samples. Pore water analysis was used to determine the pH, EC and moisture content of fly ash samples. A five step sequential chemical extraction procedure was used to establish the geochemical association of particular elements with various mineral phases. The total acid digestion test was also used to determine the total elemental compositions of the Secunda fly ash samples. The SEM results showed that the fly ashes consist of irregular and numerous spherically shaped particles. Changes (encrustations, etchings and corrosion) in the morphologies of the weathered ash particles were also observed. The XRD results revealed quartz, mullite, lime and calcite as the major mineral phases. Other minerals identified in very minor quantities in the drilled Secunda ash core that were dried prior to analysis were halite, kaolinite, nitratine, bassanite, microline. and hydrophitte. These phases may have formed during sample handling. XRF investigation revealed that the major oxides present in the dumped ash samples were SiO₂, A₂2O₃, CaO, Fe₂O₃, MgO, Na₂O, TiO₂ and the minor elements present were K₂O, P₂O₅, SO₃ and MnO. The sum of the mean values of the % composition of SiO₂, Al₂O₃, and Fe₂O₃ was 70.19 %, and 72.94 % for the two drilled ash core samples (S1 and S3) respectively, and 78.67 % for the fresh ash which shows the significant alteration of the Si, Al and Fe content in the ash matrix over time. The fly ash is classified as Class F using the ASTM C 618 standards. The loss on ignition (LOI) which is an indication of unburned carbon or organic content was 4.78 %, 13.45 % and 8.32 % for the fresh ash, drilled ash cores S1 and S3 respectively. The high LOI values for the drilled ash cores could indicate high hydrocarbon content in the ash dump because of co-disposal practises where hydrocarbon waste are included in the brine stream for disposal on the ash. While the ash samples from the surface appeared dry, moisture content (MC) analysis showed that there is considerable water entrained in the fly ash dump. The fresh ash MC was 1.8 % while core S1 ranged from 41.4 – 73.2 %; core S3 ranged from 21.7 – 76.4 %. The variations in the MC values can be attributed to uneven flow paths due to inconsistent placement conditions or variations in ambient weather conditions during placement. The fresh fly ash (n=3) had a pH of 12.38±0.15, EC value of 4.98±0.03 mS/cm and TDS value of 2.68±0.03 g/L, the pH of the drilled ash core S1 (n=35) was 10.04 ±0.50, the EC value was 1.08±0.14 mS/cm and the TDS value was 0.64 ±0.08 g/L. Core S3 (n=66) had pH of 11.04±0.09; EC was 0.99 ±0.03 and TDS was 0.57 ± 0.01. The changes in pH values can be attributed to the dissolution and flushing out from the dump basic alkaline oxides like CaO and MgO These variations in pH values shows that the fly ash is acidifying over time and metal mobility can be expected under these conditions. The large decrease of EC in the drilled ash cores S1 and S3 compared to the fresh ash indicated a major loss of ionic species over time in the ash dump. The sequential extraction scheme revealed that the elements Al, Si, Ca, Mg, Ba, Sr, Fe, Mn, Na, K, As, Pb, Cr, Mo, Cu, Ni and Zn are present in Secunda fresh and weathered fly ash and are partitioned between the water soluble, exchangeable, carbonate, iron and manganese, and residual fractions of the coal fly ash. It also showed that the trace elements As, Pb, Cr, Mo, Cu, Ni and Zn do not show permanent association with particular mineral phases as a continuous partitioning between different mineral phases was observed in the weathered drilled core. Generally, all the elements had the highest concentration in the residual fraction. But it was evident that the labile phase (water soluble, exchangeable and carbonate fractions) had fairly high concentrations of Si (± 6.5 %), Al (± 6.5 %), Ca (±10 %), Mg (± 5.5 %), Ba (± 7.5 %),Sr (± 7.5 %), Na (± 12 %) and K (± 12 %) for the Secunda drilled ash core (S1 and S3) and fresh fly ash samples. This indicates that these species can leach easily upon water ingress and could pose a danger to the environment. Na and K had the highest concentrations leached out in the labile phase in all the ash samples. The amount of Na leached out of the drilled Secunda ash core in the labile phase was 13.21 % of 18584.26 mg/kg in the five geochemical phases of core S1; and 9.59 % of 11600.17 mg/kg in the five geochemical phases of core S3 while the fresh Secunda fly ash leached out 11.28 % of 16306.30 mg/kg of Na in the five geochemical phases. This study provided significant insight into the pore water chemistry, morphology, mineralogy and chemical composition and the elemental distribution pattern of the major and trace elements in the Secunda fly ash and weathered drilled Secunda ashm core S1 and S3. Though results from XRF analysis and the sequential extraction scheme shows that Na, K, S, Ca and Mg were slightly captured from the co-disposed brine by the Secunda fly ash, these species were however released in the labile phase. Hence there was no significant retention of these species in the ash dump. The amount of these species retained in the weathered ash were (0.26 % and 0.55 %) for Na, (0.02 % and 0.34 %) for K, (0.08 % and 0.06 %) for S, (0.94 % and 0.01 %) for Ca and (0.37 % and 0.96 %) for Mg in drilled ash cores S1 and S3 respectively. This poor retention of Na K, S, Ca and Mg which are major components of Sasol Secunda brine in the drilled ash cores S1 and S3 clearly shows the unsustainability of the Secunda fly ash dump as a salt sink.